JP3255669B2 - Catalyst composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to novel catalyst compositions suitable for use in the preparation of polymers of carbon monoxide and one or more monoolefins.

[0002] A linear polymer of carbon monoxide and ethene, in which units derived from carbon monoxide and units derived from ethene are present in a substantially alternating order in the polymer, is formed from a group 8 metal and a general formula (R ¹ ) ₂ P—R—P (R ¹ ) ₂ [wherein R ¹ represents a monovalent aromatic hydrocarbon group which may be optionally polar-substituted, and R is a divalent organic bridging group] It is known that a catalyst composition containing a phosphorus bidentate ligand having the following formula can be produced by contacting a monomer at a temperature higher than normal temperature and a pressure higher than normal pressure. The bridging group R preferably contains three atoms in the bridge connecting the two phosphorus atoms, at least two of which are carbon atoms and both of which are part of a single cyclic structure. The two atoms forming the part are not in them. It was believed that a phosphorus bidentate ligand in which such a bridge R is present would provide a catalyst composition having the highest polymerization rate. An example of such a phosphorus bidentate ligand is 1,
3-bis (diphenylphosphino) propane.

A disadvantage of alternating carbon monoxide / ethene polymers is that they have a very high melting point. Processing of these polymers must be performed in the molten state with the material at least 25 ° C. above the melting point. It is known that these polymers are not resistant to the high temperatures required for their processing, resulting in discoloration and decomposition. As a solution to this problem, as proposed in EP-A-213671, the Applicants have added to their monomer mixture a [alpha] having at least 3 carbon atoms per molecule.
It has been found that the incorporation of a relatively small amount of one or more olefins (indicated for simplicity as C ₃₊ α-olefins) can significantly lower the melting points of these polymers. The more C3 ₊ alpha-olefins that are incorporated into the monomer mixture, the lower the melting point of the resulting polymer. To contain a phosphorus bidentate ligand with three atoms in the bridge,
The above catalyst composition exhibiting the highest rate of polymerization of carbon monoxide and ethene may also exhibit the highest rate of polymerization of carbon monoxide obtained by adding one or more C3 ₊ α-olefins to ethene. Was found.

[0004] Applicants have reported that carbon monoxide and C₃₊α-Oleph
Units derived from quinine are substantially alternating
Carbon and one or more carbon atoms₃₊α-olefins (ie using ethene
No) is obtained by using the above catalyst composition.
We recently did some research to find out how much we could produce.
Such polymers can actually be produced in this way.
Although this catalyst composition can be used with carbon monoxide and ethene,
Intentional and additional C₃₊In polymerization with α-olefin
Low polymerization rate compared to previously observed polymerization rates
It turned out to only show. Previously with carbon monoxide
Polymerization with ethene and one or more of carbon monoxide and ethene
C₃₊The observed observed in the polymerization with the addition of α-olefin
Carbon monoxide and one or more C₃₊Polymerization of α-olefin
, A phosphorus bidentate ligand having three atoms in the bridge
It is also confirmed that catalyst compositions containing
Was called. As described in EP-A-376 364,
Applicants continued their research on this issue and found that
Carbon and one or more carbon atoms₃₊Before the polymerization of α-olefins
When the polymerization rate of the catalyst composition described above is in a phosphorus bidentate ligand,
Monovalent aromatic R which may be more polar substituted¹hydrocarbon
A monovalent aliphatic R optionally substituted with a polar group
^TwoWhat can be raised by replacing with hydrocarbon groups
understood. Bound to phosphorus, optionally polar
Phosphorus bidentate ligand in which the monovalent hydrocarbon group which may be aromatic is aromatic
And carbon monoxide using a catalyst composition containing
Polymerization rate in polymerization with all kinds of α-olefins
Observations between the number of carbon atoms in the bridge of the phosphorus bidentate ligand
Considering the relationship, the hydrocarbon groups bonded to phosphorus
Such a catalyst composition containing an aliphatic bidentate ligand
That the same relationship holds, that is, three bridges
The highest polymerization rates can be obtained with ligands containing atoms.
That would be logical. The general formula (R^Two) _TwoP
-RP (R^Two)_TwoOf phosphorus bidentate ligands of this type with
Is 1,3-bis (di-n-butylphosphino) propane
It is.

In the course of continuing research on this subject, 2
Containing four atoms in the bridge connecting the two phosphorus atoms,
At least two of the four are carbon atoms, and
By selecting a divalent organic bridging group R ³ as the bridging group R of the phosphorus bidentate ligand such that there are no two atoms together forming part of a single ring structure, It has been surprisingly found that the activity of the last-mentioned catalyst composition among the above-mentioned catalyst compositions for the polymerization of carbon monoxide and one or more C ₃₊ α-olefins can be increased. General formula (R ² ) ₂ P-
As a phosphorus bidentate ligand having the _{^{R-P (R 2) 2}} , by selecting the phosphorus bidentate ligand having the general formula _{^{(R 2) 2 P-R}} 3 -P (R 2) 2, It has further been found that the polymerization of carbon monoxide with ethene and one or more additional C ₃₊ α-olefins also leads to an increase in the activity of the catalyst composition.
In stark contrast, this type of choice in the polymerization of carbon monoxide and ethene has been found to result in a reduction in the rate of polymerization. Finally, carbon monoxide and one or more C ₃₊
The activity of a catalyst composition containing a phosphorus bidentate ligand having the general formula (R ² ) ₂ P—R ³ —P (R ² ) ₂ in the polymerization of α-olefins and possibly further ethene is two It has been found that further improvement is achieved by replacing one of the respective R ² groups of the phosphorus atom by an aliphatic hydrocarbon group having a different number of carbon atoms from R ² and optionally polar substitution. Meanwhile, the unusual behavior of a catalyst composition containing a phosphorus bidentate ligand having the general formula (R ² ) ₂ P—R ³ —P (R ² ) ₂ in the polymerization of carbon monoxide and ethene was previously observed. Correspondingly, it has now also been found that this type of substitution causes a reduction in the polymerization rate in this polymerization. The advantageous effect on the polymerization obtained by the above modification of the phosphorus bidentate ligand can only be obtained when the catalyst composition is used for polymerizing a monomer mixture containing C3 ₊ α-olefins. Is evident.

The group VIII metal and the general formula (R ² ) (R ⁴ ) PR
³ -P (R ² ) (R ⁴ ) wherein R ² and R ⁴ are the same or different, optionally a monovalent aliphatic hydrocarbon group which may be polar-substituted, and R ³ is two A divalent organic bridging group containing four atoms in the bridge connecting the phosphorus atoms of the formula, at least two of the four atoms are carbon atoms, and Are free of two atoms that together form part of a single cyclic structure].

Accordingly, the present patent application discloses a novel bidentate ligand containing a Group 8 metal and a phosphorus bidentate ligand having the general formula (R ² ) (R ⁴ ) P-R ³ -P (R ² ) (R ⁴ ) Catalyst composition.
The present patent application further relates to polymers of carbon monoxide and one or more C ₃₊ α-olefins, and optionally to the use of these catalyst compositions in the preparation of polymers with ethene.

In the present patent application, the Group VIII metals are the iron group metals iron, cobalt and nickel along with the noble metals ruthenium, rhodium, palladium, osmium, iridium and platinum.

[0009] In the catalyst composition of the present invention, the Group 8 metal is preferably selected from palladium, nickel and cobalt. Palladium is particularly preferred as the Group 8 metal. The introduction of the Group 8 metal into the catalyst composition is preferably carried out in the form of a salt of a carboxylic acid, in particular in the form of an acetate. In addition to the group VIII metal and the phosphorus bidentate ligand, the catalyst composition of the present invention preferably also contains an anion of an acid having a pKa of less than 4, especially an anion of an acid having a pKa of less than 2. . Examples of acids having a pKa of less than 2 are mineral acids such as sulfuric acid and perchloric acid, sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid, and trichloroacetic acid.
Halocarboxylic acids such as difluoroacetic acid and trifluoroacetic acid. Sulfonic acids such as p-toluenesulfonic acid or halocarboxylic acids such as trifluoroacetic acid are preferred. The anion can be introduced into the catalyst composition either in the form of a compound from which the desired anion is separated or in the form of a mixture of compounds which upon interaction form the desired anion. Usually, the anion is incorporated into the catalyst composition in the form of an acid. If desired, anions can be included in the catalyst composition in the form of a typical metal salt of the acid or a transition metal salt of a non-noble metal. If a carboxylic acid anion is selected, the incorporation into the catalyst composition may be in the form of the acid or a derivative thereof, such as an alkyl or aryl ester,
Amide, imide, anhydride, orthoester, lactone,
It can be carried out in the form of a lactam or an alkylidene dicarboxylate. Anion is 1 for 1 g atom of Group 8 metal.
It is preferred that it is present in the catalyst composition in an amount of １００100 mol, in particular 2-50 mol. As used as a separate component, the anion of the acid having a pKa of less than 4 is present in the catalyst composition, for example by using palladium trifluoroacetate or p-p-tosylate as a Group 8 metal compound. You can also.

[0010] In addition to the Group VIII metal, the phosphorus bidentate ligand and optionally the anion of an acid having a pKa of less than 4, the catalyst composition of the present invention may also contain an organic oxidizing agent. Examples of suitable organic oxidants are 1,2- and 1,4-quinones, aliphatic nitrites such as butyl nitrite, and aromatic nitro compounds such as nitrobenzene and 2,4-dinitrotoluene. 1,4-benzoquinone and 1,4-naphthoquinone are preferred. The amount of organic oxidant used is 8
It is preferably 5 to 5000 mol, particularly 10 to 1000 mol, per 1 g atom of the group metal.

In the catalyst composition of the present invention, the phosphorus bidentate ligand is contained in an amount of 0.5 to 2 mol, especially 0.7 mol, per 1 g atom of the Group 8 metal.
It is preferably present in an amount of 5 to 1.5 mol. In the phosphorus bidentate ligand having the general formula (R ² ) (R ⁴ ) P—R ³ —P (R ² ) (R ⁴ ), the R ³ bridging group is a bridge connecting two phosphorus atoms. It contains four atoms in it, at least two of which must be carbon atoms. An example of a very suitable bridging group is a tetramethylene group. In the phosphorus bidentate ligand,
Preferably contains R ² and R ⁴ are 10 or fewer carbon atoms, respectively. As explained above, phosphorus bidentate ligands can be used with the same R ² and R ⁴ groups in the catalyst composition of the present invention. An advantageous result is that according to the invention R ²
Phosphorus bidentate ligand in which the group and the R ⁴ group are identical, for example 1,4
-Bis (di-n-butylphosphino) butane is obtained by using a catalyst composition containing the same. R ² group and R
Preference is given to using phosphorus bidentate ligands in which the ^four groups differ from one another in carbon number. In accordance with the present invention, a phosphorus bidentate ligand wherein the R ² and R ⁴ groups are mutually different alkyl groups and one is methyl, such as 1,4-bis (methyl-n-butylphosphino) Very advantageous results are obtained by using a catalyst composition containing butane.

[0012] The polymerization of the present invention is preferably carried out by contacting the monomer with a solution of the catalyst composition in a diluent in which the polymer is insoluble or almost insoluble. Lower alcohols such as methanol are very suitable as diluents. If desired, the polymerization can be carried out in the gas phase.

The C ₃₊ α- used in the production of the polymer of the present invention.
With respect to olefins, α-olefins having up to 10 carbon atoms per molecule are preferred. Preference is given to using a monomer mixture in which, in addition to carbon monoxide and the optional component ethene, only one C _{3 +} α-olefin is present. Suitable C
Examples of ₃₊ α-olefins are propene, pentene-1 and 4
-Methylpentene-1. The process according to the invention is very particularly suitable for preparing copolymers of carbon monoxide and propene and for preparing terpolymers of carbon monoxide with ethene and propene.

The amount of catalyst composition used in the preparation of the polymer can vary within wide limits. Group ^-7 metal, 10 ^-7 to 10 ^-3 g atoms, per mole of olefin to be polymerized,
In particular, it is preferred to use an amount of the catalyst composition containing from 10 ^-6 to 10 ^-4 g atoms.

The preparation of the polymer is preferably carried out at a temperature of 25 to 150 ° C. and a pressure of 2 to 150 bar, in particular at a temperature of 30 to 130 ° C. and a pressure of 5 to 100 bar.

[0016]

The present invention will be described in more detail with reference to the following examples.

Example 1 A carbon monoxide / ethene copolymer was prepared as follows.
After purging with nitrogen from a 100 ml autoclave with stirring to expel air, a catalyst solution comprising the following components was introduced into the autoclave.

40 ml methanol 0.05 mmol palladium acetate 0.055 mmol 1,3-bis (diphenylphosphino) propane and 0.1 mmol p-toluenesulfonic acid.

After injecting a 1: 1 mixture of carbon monoxide / ethene to a pressure of 40 bar, the contents of the autoclave were heated to 90.degree. During polymerization, a 1: 1 mixture of carbon monoxide / ethene was injected to keep the pressure constant. After 1 hour, the reaction mixture was cooled to room temperature and the pressure was released to terminate the polymerization. The polymer was filtered off, washed with methanol and dried.

17.7 g of copolymer were obtained. The polymerization rate was 3,300 g copolymer / (g palladium.hour).

Examples 2-5 Example 1 was repeated with the difference that the bidentate ligands listed in Table I were used instead of 1,3-bis (diphenisphosphino) propane. The yields obtained (expressed in g copolymer) and the polymerization rates (expressed in g copolymer / (g palladium / hour)) are likewise listed in Table I.

Table I Example Ligand Yield Rate 1 1,3-bis (diphenylphosphino) propane 17.7 3300 2 1,4-bis (diphenylphosphino) butane 13.3 2480 3 1,3-bis (di-n -Butylphosphino) propane 5.4 1010 4 1,4-bis (di-n-butylphosphino) butane 4.0 750 5 1,4-bis (methyl, n-butylphosphino) butane 1.8 33
Example 6 A carbon monoxide / ethene / proppentapolymer was prepared as follows. After purging with nitrogen from a 100 ml autoclave with stirring to expel air, a catalyst solution comprising the following components was introduced into the autoclave.

40 ml methanol 0.05 mmol palladium acetate 0.055 mmol 1,3-bis (diphenylphosphino) propane and 0.1 mmol p-toluenesulfonic acid.

After adding 9.3 g of propene, the temperature was raised to 90 ° C., and then a 1: 1 mixture of carbon monoxide / ethene was added to 4 parts of the mixture.
Pressure was applied until a pressure of 0 bar was reached. During the polymerization, the pressure was kept constant by injecting a 1: 1 mixture of carbon monoxide / ethene. After 1 hour, the reaction mixture was cooled to room temperature and the pressure was released to terminate the polymerization. The polymer was filtered off, washed with methanol and dried.

13.9 g of terpolymer were obtained. The polymerization rate was 2590 g terpolymer / (g palladium.hour).

Examples 7 to 13 One of the bidentate ligands also used in Examples 2 to 5 in place of 1,3-bis (diphenylphosphino) propane in some cases
Example 6 was repeated, except that one was used and the amount of propene (in g) listed in Table II was used instead of 9.3 g. The yields obtained (expressed in g terpolymer) and the polymerization rates (expressed in g terpolymer / (g palladium.hour)) are likewise listed in Table II.

Table II Example Ligand Example Number Propene Injection Yield Rate 6 1 9.3 13.9 2590 7 2 10.3 6.1 1140 8 1 10.5 (a) 29.4 5480 9 2 10.2 (a) 17.2 3200 10 3 11.5 (b) 1.2 150 11 4 10.0 4.7 880 12 4 12.3 (a) 5.8 1080 13 5 12.2 (a) 6.4 2000 (a) Instead of 40 bar, the mixture was injected until a pressure of 55 bar was obtained.

(B) The reaction time was 1.5 hours instead of 1 hour.

Example 14 A carbon monoxide / propene copolymer was prepared as follows. After purging with nitrogen and purging air from a 100 ml autoclave with stirring, a catalyst solution comprising the following components was introduced into the autoclave.

40 ml methanol 0.05 mmol palladium acetate 0.055 mmol 1,3-bis (di-n-butylphosphino) propane, and 0.1 mmol p-toluenesulfonic acid.

After addition of 10.7 g of propene,
And then injected with carbon monoxide until a pressure of 40 bar was reached. During the polymerization, carbon monoxide was injected to keep the pressure constant. After 3 hours, the reaction mixture was cooled to room temperature and the pressure was released to terminate the polymerization. The polymer was isolated by evaporation of the reaction mixture.

2.5 g of copolymer were obtained. The polymerization rate is 1
It was 60 g copolymer / (g palladium.hour).

Examples 15 to 18 The use of one of the bidentate ligands also used in Examples 4 or 5 in place of 1,3-bis (di-n-butylphosphino) propane and Table III Example 14 was repeated with the difference that the amount of propene (in g) was introduced instead of 10.7 g. Obtained yield (g copolymer)
And polymerization rate (g-polymer / (g palladium-hour)
Are shown in Table III.

Table III Example Ligand Example Number Propene Injection Yield Rate 14 3 10.7 2.5 160 15 4 8.4 6.1 380 16 4 12.0 (c, d) 2.7 510 175 59.7 (e) 8.2 490 18 5 12.2 ( f, d) 4.1 760 (c) The reaction temperature was 90 ° C instead of 60 ° C.

(D) The reaction time was changed to 1 hour instead of 3 hours.

(E) The reaction time was changed to 3.2 hours instead of 3 hours.

(F) The catalyst contained 0.11 mmol of perchloric acid instead of p-toluenesulfonic acid and also contained 1 mol of trimethyl orthoformate.

Example 19 A carbon monoxide / propene copolymer was prepared in substantially the same manner as in Example 14, with the following differences.

A) The polymerization was carried out in a 300 ml autoclave instead of 100 ml.

B) 120 ml of methanol instead of 40 ml,
1,4-bis (methyl, n-butylphosphino) instead of 1,3-bis (di-n-butylphosphino) propane
A catalyst solution consisting of butane was used.

C) 27.0 g of propene were introduced instead of 10.7 g.

D) The reaction temperature was 70 ° C. instead of 60 ° C., and e) The reaction time was 1 hour instead of 3 hours.

6.4 g of copolymer were obtained. The polymerization rate is 1
190 g copolymer / (g palladium.hour).

Example 20 A carbon monoxide / propene copolymer was prepared in substantially the same manner as in Example 14, with the following differences.

A) The polymerization was carried out in a 300 ml autoclave instead of 100 ml.

B) A catalyst solution comprising the following components was used.

120 ml methanol 0.1 mmol palladium acetate 0.11 mmol 1,4-bis (di-n-butylphosphino) butane, and 0.2 mmol p-toluenesulfonic acid.

C) 23.0 g of propene were introduced into the autoclave instead of 10.7 g.

D) The reaction temperature was changed to 80 ° C. instead of 60 ° C. And e) the reaction time was 1 hour instead of 3 hours.

7.5 g of copolymer were obtained. Polymerization rate is 7
It was 10 g copolymer / (g palladium.hour).

Of Examples 1 to 20, Examples 11 to 13
And Examples 15 to 20 are examples of the present invention. In these examples, the group VIII metal and the general formula (R ² ) (R ⁴ ) P—R
Carbon monoxide / propene copolymer and carbon monoxide / ethene / proppenta-polymer were prepared using a catalyst composition containing a phosphorus bidentate ligand having ^3- P (R ² ) (R ⁴ ). . Examples 1 to 10 and 14 are described in this patent application for comparison.

Examples 1-5 relate to the preparation of carbon monoxide / ethene copolymer. Comparing the results of these examples, it can be seen that in the catalyst composition, a phosphorus bidentate containing three atoms is in the bridge connecting the two phosphorus atoms to each other, and four in the bridge. It has been found that replacement with a phosphorus bidentate ligand containing a carbon atom results in a decrease in the rate of polymerization. This is true for both tetraaryl and tetraalkyl-bisphosphines. If the tetraalkylbisphosphine having the same alkyl group bonded to phosphorus is replaced by a tetraalkylbisphosphine having a different carbon number in the alkyl group bonded to phosphorus, the polymerization rate is further reduced.

Examples 6-10 relate to the preparation of carbon monoxide / ethene / propene terpolymer. Comparing the results of Examples 6 to 9, the tetraarylbisphosphine containing three atoms in the bridge connecting the two phosphorus atoms in the catalyst composition is replaced with four carbon atoms in the bridge. It has been found that replacement with an atom-containing tetraarylbisphosphine results in a decrease in the rate of polymerization.

A comparison of the results of Examples 10 and 11 with the results of Examples 14 and 15 shows that in the catalyst composition a tetraalkylbis containing one atom in the bridge connecting the two phosphorus atoms was used. Replacing phosphine with a tetraalkylbisphosphine containing 4 carbon atoms in the bridge increases the rate of polymerization in both the production of carbon monoxide / ethene / propene polymers and the production of carbon monoxide / propene copolymers. Is generated.

When the results of Examples 12 and 13 are compared with the results of Examples 15 and 17, tetraalkyl bisphosphine in which the alkyl group bonded to the phosphorus atom is the same is bonded to the phosphorus atom. When the alkyl group is replaced by a tetraalkylbisphosphine having a different carbon number,
It can be seen that both the production of the carbon monoxide / ethene / propantha polymer and the production of the carbon monoxide / propene copolymer result in increased polymerization rates.

The polymers prepared in Examples 1 to 20
It was confirmed by ¹³ C-NMR analysis that one was derived from carbon monoxide and the other was derived from the olefin used, and the units were composed of linear chains present in an alternating order. In the terpolymer chain, units derived from ethene and propene were present in a random distribution.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-189337 (JP, A) JP-A-64-62326 (JP, A) JP-A-62-285919 (JP, A) JP-A-59-1985 197427 (JP, A) JP-A-4-258634 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 67/02

Claims (9)

(57) [Claims] 1. A mixture comprising carbon monoxide, one or more α-olefins having at least 3 carbon atoms in one molecule (C ₃₊ α-olefins), and optionally also ethene,
Group 8 metal of the general formula ^{(R 2) (R 4)} P-R 3 -P (R 2) (R 4)
[Wherein, R ² and R ⁴ are the same or different, and are optionally a monovalent aliphatic hydrocarbon group which may be polar-substituted]
A method for producing a polymer, comprising: contacting a catalyst composition containing a phosphorus bidentate ligand having the formula: at a temperature higher than normal temperature and a pressure higher than normal pressure, wherein R ³ is two phosphorus atoms A divalent organic bridging group containing 4 atoms in the bridge connecting (where at least 2 of the 4 atoms in the bridge are carbon atoms and 4 Wherein there are no two atoms that together form part of a single ring structure). 2. The catalyst composition according to claim 1, wherein the catalyst composition further comprises an anion of an acid having a pKa of less than 4 in an amount of from 1 to 100 mol per g atom of Group 8 metal. The method described in. 3. The catalyst composition according to claim 1, wherein the catalyst composition contains a phosphorus bidentate in an amount of 0.5 to 2 mol per 1 g atom of the Group 8 metal. the method of. 4. The process according to claim 1, wherein the catalyst composition contains a phosphorus bidentate in which the R ³ bridging group is a tetramethylene group. 5. The catalyst composition according to claim 1, wherein the catalyst composition contains a phosphorus bidentate ligand in which the R ² and R ⁴ groups each contain up to 10 carbon atoms. The method described in Crab. 6. The catalyst composition according to claim 1, wherein the catalyst composition contains a phosphorus bidentate ligand in which R ² and R ⁴ are the same alkyl group. the method of. 7. The catalyst composition according to claim 1, wherein the catalyst composition contains a phosphorus bidentate ligand in which R ² and R ⁴ groups have different carbon numbers from each other. The method described in. 8. The catalyst composition according to claim 1, wherein the R ² group and the R ⁴ group are alkyl groups having different carbon numbers, and one of the R ² group and the R ⁴ group is a methyl group. The method according to claim 7, characterized in that it contains. 9. A temperature of 25 to 150 ° C. and 0.2 to 15 M
The reaction is carried out under a pressure of Pa (2 to 150 bar), and the catalyst composition is used in an amount containing 10 ^-7 to 10 ^-3 g atoms of Group 8 metal per mole of the olefin to be polymerized.
The method according to claim 1.